Germicidal detergent composition



United States Patent GERMICIDAL DETERGENT COMPOSITION Frederick WilliamGray, Belleville, N. 1., assignor to Co]- gate-Palmolive Company, JerseyCity, N. 1., a corporation of Delaware No Drawing. Application February26, 1954, Serial No. 412,937

2 Claims. (Cl. 252-106) The present invention relates to germicidaldetergent compositions containing N-chlorinated higher alkyl arylsulfonamide compounds.

In accordance with the present invention, a germicidal detergentcomposition consists essentially of from about 5 to about 95% of awater-soluble organic anionic detergent and from about 0.01 to 50% of asulfonamide having the formula:

wherein R is an alkyl group of about to carbon atoms, Ar is a benzenenucleus, and Y is selected from the group consisting of chlorine,hydrogen, alkali metal, and alkaline earth metal.

The alkyl radical on the aromatic nucleus of the sulfonamide compoundsof the present composition is straight or branched chain and containsabout 10 to 22 carbon atoms. Suitable examples of such radicals aredecyl, dodecyl, keryl, pentadecyl, hexadecyl, mixed long chain alkylsderived from long chain fatty materials, cracked parafiin wax olefins,polymers of lower mono-oleflns, etc. It is preferred that the alkylsubstituent average about 12 to about 18 carbon atoms. For example,propylene may be polymerized to the tetramer and condensed with benzenein the presence of an alkylation catalyst, e. g. a Friedel-Craftscatalyst, to yield a mixture comprising essentially the dodecyl benzenederivative which is suitable for preparation of the desired sulfonamidetype compounds.

The aromatic nucleus of the sulfonamide compounds of the presentcomposition may be mono or polynuclear and may contain othersubstituents which do not interfere with the character of thechlorinated product. Thus a variety of suitable aromatic nuclei may bederived from benzene, naphthalene, anthracene, toluene, xylene, phenol,cresols, etc., benzene being a preferred embodiment of the invention asexemplified by dodecyl benzene sulfonchloramide, keryl benzenesulfonchloramide and decyl benzene sulfonchloramide. Other suitablematerials are keryl toluene sulfonchloramide, dodecyl napthalenesulfonchloramide, decyl anthracene sulfonchloramide, and pentadecylethylbenzene sulfonchloramide.

The alkylated aromatic nucleus preferably carries one N-chlorinatedsulfonamide substituent, such as, for example, dodecyl benzenemonosulfonchlorarnide, keryltoluene monosulfonchloramide, and pentadecylnaphthalene monosulfonchloramide. However, it is also within the scopeof the invention to have poly substitution, such as alkyl aryl diandtrisulfonchloramides, suitable examples thereof being dodecylnaphthalene disulfonchloramide and keryl naphthalenetrisulfonchloramide. In particular, the higher alkyl benzenemonosulfonmonochloramides are 2,809,937 Patented Oct. 15, 1957preferred, examples thereof comprising decylbenzcnemonosulfonmonochloramide, keryl benzene monosulfonmonochloramide,dodecylbenzene monosulfonmonochloramide, tetrapropylene benzenemonosulfonmonochloramide, and the alkali metal salts thereof such as thesodium, potassium and lithium salts and alkaline earth metal salts suchas the calcium and magnesium salts. Other suitable sulfonamide compoundsare: dodecylbenzene monosulfondichloramide, keryl naphthalenedisulfonmonochloramide, pentadecyl toluene monosulfonmonochloramide andthe above-indicated salts.

The instant sulfonamide compounds may be prepared in any convenientmanner, starting with the appropriate long-chain alkyl aryl hydrocarbonor its sulfonic acid derivative. Using the alkyl aryl hydrocarbon as aninitial reactant, the suitable sulfonic acid derivative may be formed byany convenient sulfonation procedure, such as reaction with oleum orchlorosulfonic acid. These alkyl aryl sulfonic acid compounds are wellknown in the art.

The appropriate aforesaid long chain sulfonic acid may readily beconverted to an amide by treatment with ammonia. The sulfonchloramidederivative may then be produced by suspending or dissolving the saidsulfonamide in an aqueous alkaline medium and then passing chlorine gasin excess of the stoichiometrically required amount through the mixturewhile subjecting the mixture to agitation and maintaining it at aslightly elevated temperature of about 40 C. to 50 C. The chlorinereacts rapidly with the amide group and replaces at least one of thereplaceable hydrogen atoms attached thereto, the product being a solidprecipitate which may be recovered by any means suitable forsolid-liquid phase separation, including gravity settling, decantation,filtration, centrifuging, etc. The product is recovered in the form ofits salt depending upon the base used in the alkaline medium. Any

suitable alkali metal (e. g. sodium and potassium hydroxide) or alkalineearth metal base (e. g. calcium and magnesium hydroxide) may be used toform the corresponding salt. The free N-chlorinated sulfonamide may beprepared from the corresponding salt in any suitable manner, such asreacting the suitable salt with mineral acid and separating theinorganic salt formed as a by-product from the formedN-chlorosulfonamide compound. The dichlorinated derivative may beprepared by further chlorination under similar conditions.

The purified sulfonchloramide compounds and their salts may be dried,washed, recrystallized or subjected to other conventional means ofpurification suitable to such materials.

More specifically, suitable N-chlorinated higher alkyl aryl sulfonamidesmay be prepared as follows.

About 736 parts by weight of 96.5% sulfuric acid are placed ina vesselequipped with an agitator and 435 parts of alkyl benzene (prepared byalkylating benzene with a propylene tetramer) are added. The vessel iscooled so as to maintain the reactants at 20 C. to 30 C. On completeaddition of the hydrocarbon and while maintaining the temperature atabout 20 C., 1062 parts of chlorsulfonic acid are slowly added over aperiod of about 2 hours. The reaction takes place with a strongevolution of hydrogen chloride. The contents of the vessel are agitatedthroughout the entire run and for two hours after all the chlorsulfonicacid has been added, after which the mixture is allowed to settle forseveral hours. The upper layer contains the alkylbenzene sulfonylchloride in approximately yield, and is removed for further processing.

About 290 parts of the crude alkylbenzene sulfonyl chloride areintroduced dropwise into 450 parts of 28% ammonium hydroxide while thereaction mixture is thoroughly agitated and the temperature maintainedat 25 C. to 30 C. The sulfonamide separates as a whitish yellow oil. nether extraction, the sulfonamide is obtained as a pale yellow viscousoil. The yield is about 85% of the theoretical yield based on the alkylbenzene employed.

About 150 parts of the alkylbenzene sulfonamide previously prepared aremixed in a vessel with 1000 parts of sodium hydroxide. While the liquidsare agitated, about 45 parts of chlorine gas is bubbled into the mixturecontinuously over a period of 1 hours. The reactants are maintained at40 C. to 50 C. A voluminous white precipitate is formed which is allowedto settle, the supernatant liquid is decanted, and the precipitate isslurried in cold water and filtered. The product is recrystallized fromaqueous ethanol to yield a dry, stable, white material which foamsreadily and has a characteristic hypochlorite odor in an aqueous medium.The yield of the product, which is the monosodium salt of themonosulfonmonochloramide of the alkyl benzene employed is about 80% ofthe theoretical yield. The product analyzes to an active or availablechlorine content of 8.4%, a total chlorine content of 9.29%. A sodiumsalt of a monosulfonmonochloramide of an alkyl benzene derived from apropylene tetramer and having a calculated molecular weight of 240 has atheoretical calculated chlorine content of 9.4%.

The previously described process is repeated using potassium hydroxidein the place of sodium hydroxide in the chlorination step. The productis a potassium salt of the monosulfonmonochloramide of the alkyl benzenestarting material.

The previously described process is repeated using calcium hydroxide inthe place of sodium hydroxide in the chlorination step. The product is acalcium salt of the monosulfonmonochloramide of the alkyl benzenestarting material.

Jhe instant sulfanamide compounds have particular utility in the form ofdetergent compositions exhibiting superior germicidal bleaching anddetersive power. It has been found that they are compatible withsuitable detergents resulting in a product having excellent foaming andbleaching action in a variety of detergent applications. Thesechlorinated sulfonamides may be admixed with detergents selected fromthe group consisting of watersoluble organic anionic and non-ionicdetergents in any suitable proportion. Among the suitable anionic detergents are the water-soluble higher fatty acid soaps (e. g. sodiumlaurate, potassium stearate, sodium salts of higher fatty acids derivedfrom coconut oil, palm oil and tallow), an Tsulfated'andsulfonatedmrganiodetergents. Ex: amples of the latter are water-solublesalts of higher alkyl aryl sulfonate (e. g. sodiumdodecylbenzenesulfonate, sodium kerylbenzenesulfonate), higher alkylsulfate detergent (e. g. sodium lauryl sulfate, potassium cetylsulfate), sulfuric acid esters of polyhydric alcohols incompletelyesterified with higher fatty acids (e. g. sodium coconut monoglyceridemonosulfate), sulfated higher fatty acid amides (e. g. sodium lauricmonoethanolamide sulfate) etc. Among the suitable non-ionic detergentsare the polyalkylene oxide condensates with hydrophobic organiccompounds, usually of an aliphatic or an aromatic structure. Suitableexamples thereof are the higher alkyl aryl polyglycol ethers (e. g.nonyl phenyl condensed with 6 to 30 moles ethylene oxide), organic acidesters with ethylene oxide (e. g. tall oil esters with 6 to 30 moles ofethylene oxide), and polyethylene glycol ethers of polyoxypropyleneglycol having a molecular weight of about 2,000 to 10,000, etc.

Any suitable amount of the present novel sulfonamide may be admixed withthe indicated detergents provided suflicient is used to yield thedesired germicidal and bleaching properties of the composition. It ispreferred that the amount of the sulfonamide be a minor amount of 4 thedetergent composition. The amount of anionic or non-ionic detergent willusually be from about 5 to about 99% while the amount of sulfonamidewill usually be from about .01 to 50% depending upon specific effectsdesired, the balance of the composition, if any, being any suitablefiller, diluent, or builder materials.

These compositions may also be admixed with watersoluble inorganicbuilder salts, either with or without the presence of other organicdetergents. Among the suitable inorganic salts are the ter-solublesilica es (e. g. sodium and potassium silicate), sulfate salE (el g.sodium sulfate), phosphate salts, preferably the polyphosphates (e. g.sodium tripolyphosphate, potassium pyrophosphate, sodiumhexametaphosphate), carbonates (e. g. sodium carbonate), etc. Theseinorganic salts may be similarly used in any suitable proportion such asfrom about 5 to 99% of the composition. It is preferred to use howevermajor amounts of these builder salts and a minor amount of thesulfonamide.

These detersive compositions may be prepared in any desired from such astoilet soap bars prepared with a soap and/or sulfate or sulfonatedetergent base, in particulate form such as drum or spray-driedproducts, as liquids, pastes, etc.

The following examples are additionally illustrative of the compositionsof the present invention, and are not to be considered as limiting theinvention thereto:

Example I A detergent composition is prepared by mixing 8 parts ofsodium dodecylbenzene monosulfonmonochloramide with 92 parts of aspray-dried detergent composition containing 20% sodium dodecylbenzenesulfonate, about 40% sodium tripolyphosphate, 7% sodium silicate and thebalance primarily sodium sulfate. This composition has a high degree ofbleaching and germicidal power combined with a high level of detergencyand foaming power, particularly in the cleansing and laundering ofclothes. This composition containing the chlorinated sulfonamide hasmarkedly enhanced stain removal properties particularly on ink, tomatoand similar type stains, in comparison to a composition otherwise freeof said novel sulfonamide.

Example II A germicidal soap bar is prepared by mixing 2% of sodiumdodecyl benzene monosulfonmonochloramide with soap chips comprising amixture-of parts of sodium soap derived from tallow and 25 parts ofsodium soap derived from coconut oil. The resulting mixture is milledand plodded to produce bars in the customary manner. The bars soproduced are stable and retain their germicidal eflicicacy over anexceptionally long period of time.

In place of the soaps used herein, other substantially saturated soapstocks derived from vegetable or animal sources may be employed. Forexample, soaps derived from palm kernel oil, hydrogenated fish, lard,grease, and palm and cotton seed oils may be employed.

Example III A powdered bleach composition is prepared as follows:

Parts by weight Potassium salt of keryl benzene sulfonmonochloramide 25Pentasodium tripolyphosphate 30 Sodium sulfate 45 This composition hasfoaming and detersive properties and may beneficially be used directlyor in conjunction with other detergent compositions in the cleansing ofsoiled fabrics and other articles which are benefited by treatment withan oxidizing or bleaching agent. In place of the potassiumsulfonchloramide above, efiective compositions are prepared using thefree sulfonchloramide and the corresponding calcium salt.

Example IV A detergent composition having desirable bleaching andgermicidal properties has the following composition:

Parts by weight Pentasodium tripolyphosphate 40 Tetrasodiumpyrophosphate 15 Sodium sulfate Sodium salt of dodecyl benzenesulfonmonochloramide Sodium salt of dodecyl benzene sulfonic acidAlthough the present invention has been described with reference toparticular embodiments and examples, it will be apparent to thoseskilled in the art that variations and modifications can be substitutedtherefor without depart ing from the principles and true spirit of theinvention.

Having thus described the invention, what is claimed is:

1. A germicidal detergent composition consisting essentially of fromabout 5 to about 95% of a water-soluble organic anionic detergent, andfrom about 0.01 to of a sulfonamide compound having the formula:

wherein R is an alkyl group of about 10 to 15 carbon atoms, Ar is abenzene nucleus, and Y is selected from the group consisting ofchlorine, hydrogen, alkali metal, and alkaline earth metal.

2. A composition in accordance with claim 1 wherein said sulfonamide issodium salt of dodecyl benzene monosulfonmonochloramide.

References Cited in the file of this patent UNITED STATES PATENTS1,699,888 Gunzler Jan. 22, 1929 2,495,489 Van Andel Jan. 24, 19502,658,916 Krems Nov. 10, 1953 FOREIGN PATENTS 775,247 France Oct. 8,1934 802,506 France June 13, 1936

1. A GERMICIDAL DETERGENT COMPOSITION CONSISTING ESSENTIALLY OF FROMABOUT 5 TO 95% OF A WATER-SOLUBLE ORGANIC ANIONIC DETERGENT, AND FROMABOUT 0.01 TO 50% OF A SULFONAMIDE COMPOUND HAVING THE FORMULA: